Apparatus for conducting reactions in liquid phase



May 8, 1945 vy. F. CALDWELL ETAL x APPARATUS FOR CONDUCTING REACTIONS IN LIQUID PHASE Filed June 6, 1942 3 Sheet s-Shet 1 M M Y mg M N R W m NmW T A i mm? Hg W Q y 1945- w. F. CALDW-ELYL ETAL. I 2,375,730

APPARATUS FOR CONDUCTING REACTIONS IN LIQUID PHA SE Filed June 6, 1942 2 Sheets-.Shet 2 1 ma W 0 VA ma M A Z Z W dosin /7' H. DEN

. a. W 4 j ATTORNEY Plenu 8, 1945 I 2,375,730

UNI ED STATES PATENT OFFICE.

APPARATUS FOR CONDUCTING REAcri'oNs IN LIQUID/PHASE William F. Caldwell, Old Greenwich, Robert C.

Swain, Riverside, and Joseph H. Paden, Glenbrook, Conn, assignors to American Cyanamid (loaiglpany, New York, N. Y., a corporatlonot Application June 6, 1942, Serial Np. 446,156 3 Claims. (01. 23-269 This invention relates to apparatus useful in maintaining them throughoutthef reaction uncarrying out chemical reactions in liquid phase bemg particularly adapted to operate continuder pressures suffl'ciently great to keep: them in a liquid condition. Anothenobject of the, invention is to provide apparatus wherein a chemabtantsaredissolved in a solvent and caused to ously or at least substantially so. 'The appa ratus of the present invention is also useful in 6 carrying out reactions involving highly volatile liquids which at ordinary temperatures must be kept under pressure to keep them in liquid form. In many chemical reactions itis desirable and in some cases necessary to carry out the reac- 10 tion while keeping the reaction mixture in liquid phase; that is, in an easily flowing liquid'form. When using certain common chemical reactants or solvents such as liquid ammonia, liquid S02, liquid 00a, etc., which have very low boiling points it is necessary to keep the reaction mixture under pressure to maintain these chemicals in a, liquid form at normal room temperature. Whenemploying other highly volatile solvents or reactants at elevated temperatures it is also 29 generallynecessary to keep the reaction mixture under pressure to prevent vaporization of the volatile constituents of the reaction mixture. Keeping the solvent from boiling away is necessaryv in those reactions in which-a reaction prodical reaction may be conducted, the reaction product separated and the unreacted constituents returned to the process without loss. Still another object of the invention is to provide apparatus particularly adapted to be operated in a continuous or substantially continuous manner wherein the reaction mixture is maintained under pressure at all times, the reaction product separated and the mother liquor returned to the process for reuse therein. Still another object of the invention is to provide apparatus wherein chemical reactions may be carried out economically with high overall yields and with the avoidance of undesirable by-products which might be formed, in the reaction and contaminate the product. Other objects of our invention will appear hereinafter.

Although the apparatus to be specifically described herein is useful for carrying out a wide variety of chemical reactions in liquid phase. the apparatus is particularly useful when emf rprecip telemniits mother liquor ploying highly volatile" solvents such as CO2, S02 and separated therefrom by {tramwayand ammonia in liquid phase at roomtemperaa ly important where unreacted constituents remain in the liquid since evaporation of their solvents would cause their deposition 30 and contamination of the reaction product,

n till other chemical reactions certain re-' mixture under pressure at all times it is possible to employ the apparatus with many volatile chemical substances. The apparatus is best 7 l, N suited, however, for those reactions in which-a mixtureaoi reactants in liquii form is heated react forming an insoluble product. In some under pressure for a length of tinre necessary to such cases the reaction is otpai ried to cdffi form a reaction product. which product is inglgtiqn eitheabymperafifin c the laws of chemsoluble upon cooling the reaction mixture. The ical equilibrium or by'express design of the.opmanufacture of guanidine nitrate by heating erator, and it becomes advisable to recover the ammonium nitrate with dicyandiamide or cyanunreacted constituents with their solvent and amide in water or aqueous ammonia solution reuse themin the process. A similar case arises 40 may be mentioned as an example of such a where an excess of aparticular chemical is 'mainprocess which can be very conveniently carried tained in the reaction mixture to provide a, high out in our apparatus. Another process which concentration of a particular ion or foran may be carried out in our apparatus to great ous p rpose. V advantage is the preparation of melamlne by For reasons ofeconomy it is also desirable to heating dicyandiamide dissolved in liquid ama carry out chemical reactions in a continuous or monia a d cribed nd c a 111 1 n r substantially continuous manner so that a maxins applicat on Seri l NO- 4 June 7111111111 1' pr duction will be achieved with a mint 1942. p The preparation oi other chemicals may also be carried out in' our apparatus with or without suitable modifications thereof.

Our invention will now be described in greater particularity by reference to the drawings which show one of the prefered embodiments thereof; Inthe drawings: r Fig. 1 is a perr pective view of apparatus parfrom the process. V

One of the objects of the present invention is therefore to provide particularly adapted to handle hiahly volatile liquids while 55.

tureE or IiTgherT Bysmaintainingfithe:ceaction embodies novel and useful features, it is described and claimed more particularly in the application of one ofus, William F. Caldwell, Se-

- filter is also new and possesses novel and useful features, and is described and claimed more spel mothe liq or tan 'June 6, 1942.

high pressure pump 4, reaction tubes 6, cooling material, and is also adapted to be operated unbe set to relieve the pressure in the tank at whatlocity flow from the inlet pipe may be provided 2 aavskao ticularly suited for the production of melamine by heating dicyandiamide dissolved in liquid as in the drawings, may bedrilled holes: or when the material being dissolved is of small particle ammonia; size, the pipe with suitable perforatlons'therein,

Fig. 2 is an elevational view with parts out may be covered with filter cloth of cotton, stainaway showing details of the dissolver 2 of Fig. 6 less steel, woven glass, or other corrosion-resist- I. Since this particular dissolving apparatus ant material. M

The storage tank 3 is simply a pressure vessel of corrosion-resistant material with heating or cooling coils 38, a sampling line 31, inlet line 38,

outlet line 39 and pressed equalizing line 40, The

function of this vessel is to hold a body of the liquid reaction mixture so that the process may be operated continuously while another batch of solution is being prepared in the dissolver, and

rial No.446,15'7, filed June 6 1942.

Fig. 3 is an elevational view with parts cut away showing details of the filter employed in the apparatus shown,in ll ig. 1. This particular- Since the apparatus to be specifically described is particularly useful in the production 01' melamine by heating dicyandiamide dissolved in liquid Referring to Fig. 1, there is shown a mother am onia. the o e atio of t e apparatus i o liquor tank I, a dissolver 2. a storage tank 3, junction with the preparation of this material will be described. The ammoniacal dicyandiamide tank 1 and filters 8 and s, which parts include s ut o us d i h p o ess m y bep pa ed a the most essential elements of the apparatus to l be described. With all valves closed, the cover 20 of the dis- Mother liquor tank i is simply a closed preslv r i removed nd Weighed n y f surevessel of stainless steel, or other strong, corcyflndiamide is added 0 the Vessel- T cove! rosion-l'esistant material, and is fitted with heati then t tly s l d a d v s 41 and I! op ing or cooling coils ll', sampling tube It, inlet Valve 43 of the mother liquor tank, which conline 14, outlet line It, pressure equalizing line tains a quantity of mother liquor or liq i mit and circulation line 11. As will appear 'hereso n a, i ope d valve 4 i partly ope dinafter, this tank serves the principal function Circulating D 46 15 t Started a ammoof holding the mother-liquor recycled from the ni al liquor withdrawn from the mother liq process, tank throughvalve 43, and line 41, and pumped The dissolving tank 2 is shown in detail in through li s 8. and '49. valve 4| and line 21' F1g -2 a reference is made theret T1115 yes into the dissolver. As the liquor istorced through sel is constructed of strong, corrosion 'resistant the Openings s- 2) 0f the, inlet tube in the dissolver, it is given a circular motion. The swirling liquor in the tank dissolves part of the dicyandiamide and leaves throughoutlet line 3|.

cifically in the copending application of one of us, William F. Caldwell, Serial No. 446,159, filed der pressure. It is fitted with an easily removable cover 20 which can be takenofi to. permit the introduction of chemicals. A similar closure The circulatmn or ammoniacal uqum' through the dissolver is maintained until a sample of liquor 2| may be provided at the lower end-of the tank withdrawn from the system shows that it conand fitted with a drain pipe 22 and valve 23 which permits cleaning of the vessel when dehams summer; dicyandiamide the P sired. Heating or cooling coils 24 may be fitted that is from 9 25m 70% dicyandia'mme n in the tank as indicated. Relief valve 25 is also 4.3 the total i t r e li uo In order to hanprovided with an outlet line 25 to some pointrea larger me f r, Valv is'p i -l y movedfrom'the operating zone. This valve may Pened as Previously mentioned and pfllt 0f Th liquid reeotion' inedium or liquid reactants the liquor contained therein- W the liquor ever valued med necessary b line Qr mtmu uoftinlfllifiuih line H, where it mixes with may be introduced into the tank through inlet a has been built up desired concentration pipe The pipe 21 enters the dissolve, dicyandiamide, the valve ll is closed and the through a bushing 28 welded to the inlet pipe. liquor remaimns. 1n the dissolve-r. is Pumped into Thei assembly is then tightly screwed into a the mother tank- Valve n m men he threaded hole tapped in the tank desire-rm, In closed and the cover of remhavdindf' .side the dissolver, the inlet pipe is positioned -n ell-additional charge of dlcymdlamme added- 'substantially'parallel to the axis of the tank and ir desiredamountg thegliquor in the mother is preferably close to its wall. Inlet pipe 21 is l rt m n w llr n i fiesmes closed at its lower end 29 and has a series of it-closing valve 44 and 09 1 v lve 5 spaced openings 30, as shown in the drawings, 00 -l l e equalizing line I, w suitably D *positioned in such away that the liquid passing. tionedvalves Q2. 53 1 provi edln he into the dissolver is forced from the inlet i e system t ali t e p s ures bet een the in a strong. stream, substantially tangential to ar tanks. thus facilitating discharge of liqthe wallet the tank. Drilled holes, slits or open,- Q from 9 th as desired- 8 ings of other shapes designed to givea high veo5 glasses ,(not o 0f Wilmer be Prmded on each of the. tanks to'indicate the'level oi the liquid contents'tlierein.

Having thus obtained, an ammoniacal solution andpositioned so as to discharge the incoming liquor in a tangential direction with respect to the walls of the dissolver. of dicyandiamide of-desired strengtmlthe solu- An outlet line 3| enters the dissolver from the -;0 tion is withdrawn through. valve 38, line t bottom through a bushing 32. as shownin the the e pressure pump 4; which forces the soludrawings. This outlet pipe is also positioned subtion throu h line I and the reaction tubes stantially parallel with the axis of the'tank, is The reaction tubes y insist Simply Of 7 closed at its upper end as and has a number or less e ip rm s a reaction zone in which spaced outlet holes 34. These outlets 'maybeslits T5 h n e s n to elam e occurs T v nes the circulating liqu g return ate the mother-liqa may be heated by steam or Dowtherm vapors flowing through header 63 into the jackets 84 surrounding the reaction tubes. The condensate may be removed through header 65 as shown. The size and length of the pipes forming the 'eaction zone are dependent upon the capacity of the apparatus and should be of sufiicient volume to allow the ammoniacal liquor to remain in the reaction tubes at 110-160 C. for -60 minutes. Of course, when employing the apparatus for carrying out other reactions, different temperatures and reaction times will be found necessary. Accordingly, the size and length of the reaction tubes will be governed by the particular reaction being carried out therein. A section of the tubing provided with a cooling jacket may in some cases be desirable.

After passing through the reaction tubes, the

liquor is discharged into a cooling vessel I; The

particular cooling vessel shown is a pressure autoclave fitted with cooling coils 1 2, through which cold water or brine may circulate, and a powerful agitator 73. The degree of cooling in the cooling vessel should be sufiicient to cause the crystallization from the solution of most of the melamine or other crystalline productin other processes in the ammoniacal liquor, without caus- 3. Referring to this figure it will be seen that the filter consists essentially of a substantially cylindrical casing of relatively small internal diameter, strongly constructed of steel or a corrosion-resistant alloy. The casing may be fitted with a cooling jacket 86 forming a space 81 in shown. The tubular filtering element may coniprise a pipe closed at its lower end 89 and .having perforations therein of desired shape.

- The perforated pipe may be covered with stainless steel screen 9| of suitable mesh which may in turn be covered with filter cloth 92. The filtering element is held in place by bushing 93, screwed into the casing head 84, engaging ing the precipitation of unreacted dicyandiamide and intermediate conversion products. In the preparation of melamine, temperatures ranging from 10 to about 30 C. have been found suitable for this purpose. In order to reduce the working pressure in the cooling vessel it is desirable in some cases, particularly in the manufacture of melamine, to place a pressure relief valve 10 in the line before discharging the liquor into the cooling vessel. This makes it possible to build the cooler and filter of lighter weight materials.

This relief valve may, however, in some cases 'be located on the cooling vessel itselfyon the line to the filter, or even after the filter ifdesired. Ordinarily in the manufacture of melamine, the pressure in the cooling tank ranges from about 200 to 600 pounds per square inch.

As the pressure in the cooling vessel is ordinarily considerably lower than the pressure in the reaction tubes, failure of the relief valve to close would result in a decrease of pressure in. the reaction zone with'vaporization of the ammoniacalliquor. Should this happen, melamine would deposit in the tubes and might prevent further circulation of liquor. To avoid this possibility, we maintain a body of ammoniacal liquor in vessel 80. Ordinarily this vessel is kept about halffull ofammonia liquor with an over-' ,iying body of nitrogen or other inert gas, the

relative amounts of which may be determined by means of a sight glass BI. Inert gas may be supplied as required through line 82. Should the relief valve remain open fora period of time 'longer than is necessary to relieve the pressure.

, in the reaction tubes, the inert gas over the body of ammoniacal liquor in vessel 80 forcesthis liquor into. the reaction zone through line 83 at -.a pressure'sufiiciently high to prevent vaporization' of ammonia therein. Accordingly it will be seen that this arrangement is of importance in maintaining continuousflow of liquor through the reaction zone. This .system'also has the further function of acting as a surge tank in absorbing hydraulic impulses :transmitted to the liquor by the reciprocating high pressure pump 4.-

lugs which are an integral part of the filtering element. A suitable gasket 96 is provided to insure a tight closure of the filter. The filtering element continues through the bushing 93 as an imperforate pipe 91, and may-connect to a lead-off filtrate pipe 98, by means of a union or in the manner shown in the drawings.

The mother liquor with suspended melamine therein enters 'thefilter through line 89, tangentially as shown. The liquor is given-a swirling motion in the filter which tends to throw the. particles of melamine to the outer walls of the filter away from the filtering screen thus decreasing the tendency of the filter cake to build up on the'filteringelementj The liquor passes through thefilter cloth into'the pipe 88 and out into line 98 through valve I00, relief valve IIII and is then returned to the mother liquor.

liquid ammonia, passed throughline I06, valves I01 and I08 into the filter. Liquid ammonia passes through the filtering element and out through line I09. The ,wash liquor may be colleeted in a separate vessel (not shown) or may be added to the liquid in the mother liquor tank as make-up ammonia through valves 100 IIII and line I4.

The washed melamine may then be discharged from the filter by merely opening valves I08 and II II. Opening of the filter to the atmosphere releases the pressure on the ammonia in the filter cake, causing it to vaporize and blow' out of the filter carrying with it the melamine crystals. We

* have found that while the amount o1 ammonia The crystals rormed in the mother liquor upon cooling are removed by filtration in one of the specially designed filters shown in detail in i in the melamine filter cake is relatively small,

it is nevertheless sufiicient to thoroughly disin- I .tegrate the cake and force it from the filter. v Compressed air may also be utilized to blow the filter cake from the filterit desired. -When the filter 9 is filled, the flow of mother liquor with its melamine is changed back to filter l and the filter cake in filter l'is washed and the melamine discharged in the manner just described.

The melamine discharged from the filter is recovered intank III which is ordinarily main-. tainedabout half full of water. Afterthe melaas shown.

this operation valve m is closed; valve I22 is opened; and circulatis withdrawn fromthe discharge tank through line I24 and forced through lines I25 and 125 back into the tank tangentially The swirling motion thus created melamine with the water slurry of melamine charged, and dried. 1

Although we have described our new apparatus with particular reference to the production of The melamine mine has been blown into the water, the valve ing pump I23 placed in operation. -The aqueous 'Aiter a few minutes of melamine, it will be understoodthat many obvious modifications'may be made therein by those skilled in the art to adapt it to other particular processes without departing from the essential a iovel features thereof as pended claims.

set forth in the ap- What We claim is:

l 1. Apparatus for conducting chemical reactions in liquid phase under pressure comprising a series of elements connected in a circuit .for successive functioning in continuous flow including a dissolving vessel constructed for the admission of solids and retentionof pressure, an-

accumulator vessel, a pump, a jacketed pip of relatively long extent, a reducing valve, a vessel fitted with. agitating and'heat exchange means, a closed filter, and a. retum filtrate conduit.

2. Apparatus forconducting chemical reacasvavao tions' in liquid phase under pressure comprisin a series of elemeuts'con'nected in a circuit for successive functioning in continuous flow including-a dissolving vessel constructed for the admission of solids and retention of pressure, a return filtrate pressure vessel, pipes constituting a. circulation system connecting said dissolving vessel and return filtrate vessel, a pump in said system for circulating liquor between the vessels and to an accumulator vessel, a second pump, a jacketed pipe of relatively long extent; a reducing valve ,discharging directly into a vessel fitted with agitating and heat exchange means, a olosedfllter, and a return filtrate conduit.

3. Apparatus for conducting chemical reactions inliquid phase under pressure comprising a series of elements connected in a circuit for successive functioning in continuous flow including a dissolving vessel constructed for the admission of solids and retention of pressure, a return filtrate 'pressure vessel, pipes constituting a circulation system connecting said dissolving vessel and return filtrate vessel, a pump-in said system for circulating liquor between the vessels and to an accumulator vessel, a second pump, a jack- .et'ed pipe of relatively long extent, a surge tank between said pump and jacketed -pipe, a reducing valve discharging directly into a vessel fitted with agitating and heat exchange means, a closed filter, and a return filtrate conduit.

WILLIAM F. cmunwrcrn- ROBERT c. swam. JOSEPH H. PADEN. 

